Monoazo dyestuffs



United States Patent It has been found that valuable new monoazo dyestuffs are obtained by coupling diazotised 1-amino-2-cyano-4- nitrobenzene or 1-amino-2,4-dinitro-6-halobenzene or 1- amino-2-cyano-4-nitro-6-halobenzene with a coupling component of the formula CHzCHzC 0 CR2 O Rs NH-Ac (I) in p-position to the CHgCHgC O 0 R:

group.

In the general formula R stands for hydrogen, halogen, alkyl or alkoxy, R stands for a radical C,,H R represents hydrogen, C,,H a cyanoethyl group or a group CH CH COOR n is a number from 1 to 5, and Ac represents the acid radical of an. optionally further substituted aliphatic carboxylic acid. The novel azo dyestufis shall be free from sulphonic acid and carboxylic acid groups.

The coupling of the starting components proceeds in the usual way in preferably acid, aqueous or aqueousorganic medium.

Among the 1-arnino-2,4-dinitro-6-halobenzenes or 1- amino-2-cyano-4-nitro-6-halobenzenes to be used asrdiazo components, the 6-chloro and 6-bromo compounds are preferably used. Suitable coupling components of the general Formula I are, inter alia, N-( 2methoxy-5'- acetylaminophenyl)-B-aminopropionic acid methyl ester and -ethyl ester, N-(3'-propionylaminophenyl)-B-arninopropionic acid-methyl ester, -ethyl ester and -pr0pyl ester, N-methylor N-ethyl-N-(3'-acetylaminophenyl)-fi-aminopropionic acid methyl ester or -ethyl ester, N-cyanoethyl- N- (3 '-acetylaminophenyl -,B-aminopropionic acid-methylor -ethyl ester, N-(3-acetylaminophenyl)-N-B-carbomethoxethyl-B-aminopropionic acid methyl ester, N-(2'- methoxy' acetylaminophenyl)-N-;8-carboethoxyethyl- B-aminopropionic acid ethyl ester, N-ethyl-N-(2'-ethoxy- 5' acetylaminophenyl) fl aminopropionic acid methyl ester, N A (2-ethoxy-5-acetylaminophenyl -fi-aminopropionic acid methyl ester, N- (3'-chloroacetylaminophenyl)-N-methyl-fi-propionic acid methyl ester, N-(3-- cyanoacetylaminophenyl) B aminopropionic acid ethyl ester and N-(3'-hydroxyacetylaminophenyl)-}8-aminopropionic acid methyl ester, N- (3' carbomethoxyaminophenyl)-N-ethyl-B-aminopropionic acid methyl ester and N-(3'-ureidophenyl)-fi-arnino-propionic acid methyl ester.

3,406,165 Patented Oct. 15, 1968 According to one variation of the process of production the new dyestuffs can also be formed by using instead of coupling components of the Formula I, with one or two -CH CH COOR groupings, azo components which contain one or two ,CH CH COOH groups, and esterifying these, after completion of the coupling, with a lower aliphatic alcohol. Since this reaction is performed in general in the presence of acid catalysts, hydrolysisof the NH-Ac groups of the azo component can take place.

The resulting NH group can, however, be subsequently acylated again and converted into a NH-Ac grouping.

The new dyestufi's, which are devoid of sulphonic acid and carboxylic acid groups correspond to the general formulae NH-Ac CN Gaga wherein R denotes a halogen atom, R stands for hydrogen or halogen, among halogen preferably Br or Cl, and R R R and Ac have the aforesaid significance are of low or no solubility in water. They are especially suitable for dyeing and printing hydrophobic materials, in particular for dyeing textile materials from aromatic polyesters, such as polyethylene terephthalates, polyamides, cellulose esters and the like. On polyethylene terephthalate fabrics, dyeings areattained with very good fastness properties, especially good fastness to light, wet processing and sublimation.

The following examples are given for the purpose of illustrating the invention.

EXAMPLE 1 26.2 grams of 2,4-dinitro-6-bromaniline are dissolved with stirring, at 0-5 C. in 200 g. of concentrated sulphuric acid, and diazotized by the addition of 17 ml. nitrosyl sulphuric acid (100 ml. correspond to 42 g. of nitrite).

No: R /CHCH$COOR1 OzN- N=N N\ Ra and H-Ac

The diazonium salt solution is poured with stirring into a solution of 26.6 g. of the compound of the formula OCH:

NHCgH C O 0 CH NHCOCH:

3 EXAMPLE 2 26.2 grams of 2,4-dinitro-6-bromoaniline are diazotizled according to the method given in Example 1. The diazonium salt solution thus obtained is combined with a solution in glacial acetic acid of a coupling component which was prepared from 27.5 grams of the compound of the formula (IHI a NHOCCH:

4 EXAMPLE 3 A mixture of 85 grams of glacial acetic acid and 40 grams of propionic acid are allowed to run below 15 C. into 17 ml. of nitrosyl sulphuric acid (100 ml. of which correspond to 42 grams sodium nitrite). The mixture is then cooled down to 5 C. and 26.2 grams of 2,4-dinitro- -bromoaniline added thereto at this temperature. The reaction mixture is stirred at -5 C. for further 4 hours and excess nitrite destroyed by means of urea. Into the solution of the diazonium compound thus obtained a solution in glacial acetic acid and propionic acid of a coupling component is added which was prepared by boiling 18 grams of 2-amino-4-acetylamino-l-methyloxybenzene with 18 grams of acrylic acid methylester and 5 grams of glacial acetic acid for 48 hours. The reaction mixture is then neutralized to pH 6 and the precipitated dyestulf filtered with suction and dried; it has a similar shade, similar fastness properties and an equally good drawing power as the dyestutf of Example 2.

In anologous manner the following dyestuffs are obtained from the corresponding diazo and coupling components, which dye polyethylene terephthalate fabrics in the given shades:

Br OCH:

a a 4 OzN N=N N\ CgHrC O O CH; NO:

Navy blue.

NH C 0 CH3 Br 0 CH:

CzH4 C O O C H: 5 OzN N=N N\ Greenish blue.

, I I 021146 0 0 CH3 N O: NH0 0 CH3 /C:H4C O 0 CH3 0 om N=NC -N Violet.

(EH40 O 0 CH3 N 0 NH0 0 0 Ha B1 0 C H1O H; H

7 OzN -N=N N Greenish blue.

C 9H4 C O O C Ha N O NBC 0 C HI Br 0 CH0 8 OzN N=N N DO.

I CaHtC 0 O CH; N O; NHC O CH;

B r OCH:

Calls 9 OzN N=N N DO.

I CgH4GOOCH; NO: NHCOCHaOH B1 OCH;

/C:H4COOCH3 10 OgN N: N\ Blue.

I H N O NHCOCHsOH Br 11 OzN-C N=NC -N (C:H|CO0CH3)1 Bluish violet.

I I V I J WV NO: NHCOCHaCl B1 0 CgHs /C:Hs 12 0 ;N N=N -N Grcenlsh blue.

I I N 0 NHCOCHzCN EXAMPLE 13 grams of thedyestutf of the formula Br OCH;

I 'r s OgN N N\ CzEhCOOH N02 NHCOCHQ v C2H4C O 0 CH N02 NHCOCH: I

dyes polyester fibers in navy blue shades.

6 diazotized at 0-5 C., while stirring, by the addition of 17 ml. of nitrosyl sulphuric acid (100 ml. correspond to 42 g. of nitrite). The diazonium salt solution is poured into a solution of 26.6 g. of the compound of the formula OCHg C H C 0 0 CH NHCOCHa in dilute sulphuric acid and ice. The solution is then neutralised to a pH of 5.5-6 first with a caustic soda solution and then with sodium acetate, filtered off with suction, washed and dried.

The resulting dyestufi is a black powder, which dissolves in organic solvents with a blue colour. Brought into line dispersion by means of suitable agents, the dyestuff dyes polyethylene terephthalate fibres in blue shades with good fastness to sublimation, washing and light.

' In analogous manner there are obtained'from the corresponding diazo and coupling components, the following dyestuffs which dye polyethylene terephthalate fabrics in the given shades:

CnHs I 17 OgN N=N N I ON 1s OINGN=NONUMI4O o 0 out), 1 CN HNC2H4COOGH Blue.

NHCOCHa OCH;

Greenish blue.

C H4CO O CH: NHC OCHz Bluish violet.

NH 0 0 on.

c1 c1 19 O;NON=N NHCHzCHzCOOCH Reddish blue.

I CN Nnoocrn C1 CH: 20 o.NON=NC NHoH,oHro0ooH3 Violet.

l I CN 7 NHOCCH:

EXAMPLE 14 minutes in about 1000 ml. of a gently boiling bath with i 4 ml. of a caustic soda solution (38 B.), 2 g. of sodium bisulphite and 1 g. of a polyglycol ether of a fatty acid amide.

A dark blue dyeing is thus obtained with a very good fastness to sublimation.

EXAMPLE 15 19.75 g. of 2-cyano-4-nitro-6-chloroaniline are dissolved in 200 g. of concentrated sulphuric acid, and

EXAMPLE 21 100 grams of polyester fibres are dyed for one hour at 125 C. in a dyebath of 1000 ml. adjusted with dilute sulphuric acid to a pH value of 4 to 4.5 containing in addition to 1.5 g. of the finely dispersed dyestuff of Example 14, 3 grams of a Weakly anion-active alkylphenyl polyglycol ether sulphate. The dyeing is then rinsed and, in order to improve the fastness to rubbing, treated for 20 to minutes in about 1000 ml. of a gently boiling bath with 4 m1. of a caustic soda solution (38 B.), 2 grams of sodium bisulphite and 1 gram of a polyglycol ether of a fatty acid amide.

A blue dyeing is thus obtained with a very good fastuess to sublimation.

EXAMPLE 22 19.75 grams of 2 cyano 4 nitroaniline are dissolved in 200 g. of concentrated sulphuric acid and diazotized with stirring at 0 to 5 C. by adding 17 ml. of nitrosyl sulphuric acid ml. of which correspond to 42 g.

of sodium nitrite). The diazonium salt solution thus obtained is poured into a solution of 26.6 grams of the coupling component of the formula of Example 24, 3 g. of a weakly anion-active alkylphenyl polyglycol ether sulphate. The dyeing is then rinsed and, in order to improve the fastness to rubbing, treated for 20-30 minutes in about 1000 m1. of a gently boiling bath ing in addition to 1.5 g. of the finely dispersed dyestuff 75 OCH I a ORHE 5 with 4 ml. of a caustic soda solution (38 B.), 2 g. of sodium bisulphite and 1 g. of a polyglycol ether of a fatty acid amide. NHGOCH, H A dark blue dyeing is thus obtained with a very good in dilute sulphuric acid and ice. The reaction mixture is i z subhmatlon' then neutralized to pH 5.5-6 by adding first soda lye 10 1 A ound of th f m l and subsequently sodium acetate. The precipitated dyeco 9 e or stuif is filtered with suction, washed and dried. The dye- RI CH CH 0 00B stuff is a black powder which dissolves in organic solvents a a 7 with blue colouration. If it is finely dispersed by means of suitable dispersing agents it dyes polyethylenetere- R; phthalate fibres blue shades having good fastness to sub- NH-Ac limation, washing and light. wherein.

The dyestutfs listed in the following table are prepared in analogous manner from the corresponding diazo and A Is a member Selected from the group conslstmg of azo components; they are useful for the dyeing of hydro- N01 N01 ON phobic fibre materials whereupon shades with good fastness to light wet processing are obtained; the dyestuffs DIN OIN yield on polyethyleneterephthalate fabrics the shades indig cated below. Y 1

001115 23 O:NC -N=N NHC:PLCOOCH; Reddish blue.

CN Nuooom OCH:

C1115 24 0,N-QN=N -N\ Blue.

| CaHcCOOCHr CN NHCOCH:

25 omOrwuQ-mmmoooom Blulsh violet.

(IJN NHCOCH:

0:115 26 om N=NN\ Violet.

CzHrCOOCHa N NHCOCH:

02H; 21 0:N- N=NC N D0.

C3HCOOC2H5 N NHCOOCH:

CgHs 2s om -N=N N\ no.

C:H4COOC:HI N NHCONH:

CH: 29 o,N N=N N Do.

| CzHrCOOCHa CN NHCONHOH:

ON 01 3o OQN N=N NHCH:CHaCO CHa D NHOCCH;

CN CHI 31 0;N -N=NONHCHNH: O CH: D

7 l IHOCCH| EXAMPLE 32 ON CN 211 l ir R is a member selected from the class consisting of hydrogen, methoxy, ethoxy and chloro;

R is the group having the formula C H R is a member selected from the class consisting of hydrogen, cyanoethyl, CH CH COOC,,H and -C I-I wherein n is an integer of 1-5; and Ac is a member selected from the group consisting of unsubstituted lower aliphatic carbonyl having 2-3 carbon atoms, chloro substituted lower aliphatic carbonyl having 2-3 carbon atoms, cyano substituted lower aliphatic carbonyl having 2-3 carbon atoms, hydroxy substituted lower aliphatic carbonyl having 2-3 carbon atoms, methoxy carbonyl, amino carbonyl and methylamino carbonyl; the compound being free of sulfonic acid and carboxylic acid groups. 2.

| /CH:CH;COOR

l 0112011200012 A NHCOCH;

wherein A is bromine or chlorine; R is lower alkyl.

3. The dyestuff of the formula l CQH4COOCH N02 NH-COCHa 4. The dyestufi of the formula NHCOCH3 5. The dyestuff of the formula NHCOCHa CzHqC O OCHa 6. The dyestuif of the formula 7. The dyestutf of the formula NOCOCHz 8. The dyestuif of the formula 1 NHCOCHa 9. The dyestuff of the formula NHCOCHa 10. The dyestuff of the formula 11. The dyestuff of the formula NHOOCHa References Cited UNITED FOREIGN PATENTS Great Britain. Great Britain.

CHARLES B. PARKER, Primary Examiner.

D. M. PAPUGA, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,406,168 October 15, 1968 Gunther Schmidt It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below: Column 5, lines 30 to 36, the right-hand portion of the formula should appear as shown below:

Column 9, lines 38 to 44, the formula should appear as shown below:

Column 12, line 32, "118" should read 11H Column 15, line 5, "01-" should read B- Signed and sealed this 24th day of February 1970.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. WILLIAM E. SCHUYLER, JR.

Attesting Officer Commissioner of Patents 

1. A COMPOUND OF THE FORMULA 